JPH10292010A - Preparation of fluorine-containing elastomer having unsaturated bond - Google Patents
Preparation of fluorine-containing elastomer having unsaturated bondInfo
- Publication number
- JPH10292010A JPH10292010A JP8761397A JP8761397A JPH10292010A JP H10292010 A JPH10292010 A JP H10292010A JP 8761397 A JP8761397 A JP 8761397A JP 8761397 A JP8761397 A JP 8761397A JP H10292010 A JPH10292010 A JP H10292010A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- containing elastomer
- adhesive
- unsaturated bond
- adhesive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、不飽和結合を有す
る含フッ素エラストマーの製造法に関する。更に詳しく
は、電子材料用接着剤の有効成分などとして用いられる
不飽和結合を有する含フッ素エラストマーの製造法に関
する。The present invention relates to a method for producing a fluorine-containing elastomer having an unsaturated bond. More specifically, the present invention relates to a method for producing a fluorine-containing elastomer having an unsaturated bond, which is used as an active ingredient of an adhesive for electronic materials.
【０００２】[0002]
【従来の技術】近年、耐熱性接着剤、特に有機系耐熱性
接着剤の開発が進められている。有機系耐熱性接着剤と
しては、ポリベンゾイミダゾール系、ポリイミド系、ポ
リアミドイミド系、フッ素樹脂系、シリコーン系、エポ
キシフェノール系、エポキシノボラック系、エポキシア
クリル系、ニトリルフェノール系等のものが挙げられる
が、中でもポリイミド-ポリベンゾイミダゾール系の接
着剤は、すぐれた耐熱接着性を有することで注目されて
いる。2. Description of the Related Art In recent years, development of heat-resistant adhesives, especially organic heat-resistant adhesives has been advanced. Examples of the organic heat-resistant adhesive include polybenzimidazole-based, polyimide-based, polyamide-imide-based, fluororesin-based, silicone-based, epoxyphenol-based, epoxy novolak-based, epoxyacryl-based, and nitrilephenol-based adhesives. Among them, polyimide-polybenzimidazole-based adhesives have attracted attention because of their excellent heat-resistant adhesiveness.
【０００３】しかるに、このポリイミド-ポリベンゾイ
ミダゾール系の接着剤は、接着性を発現させる硬化時の
温度が高く、また反応時に水を発生させるなどの問題点
があり、長期耐熱性、接着性、硬化条件などの点におい
てすべて満足される特性を有する耐熱性接着剤は未だ得
られていない。[0003] However, this polyimide-polybenzimidazole-based adhesive has problems such as a high temperature at the time of curing for exhibiting adhesiveness and generation of water at the time of reaction. A heat-resistant adhesive having all satisfactory properties in terms of curing conditions and the like has not yet been obtained.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、耐熱
性の要求される電子材料用接着剤の有効成分などとして
用いられる不飽和結合を有する含フッ素エラストマーの
製造法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing a fluorine-containing elastomer having an unsaturated bond, which is used as an active ingredient of an adhesive for electronic materials requiring heat resistance. .
【０００５】[0005]
【課題を解決するための手段】かかる本発明の目的は、
低分子量含フッ素エラストマーを水酸化カリウムのアル
コール溶液によって脱フッ化水素化反応させ、不飽和結
合を有する含フッ素エラストマーを製造することによっ
て達成される。SUMMARY OF THE INVENTION The object of the present invention is as follows.
This is achieved by subjecting a low molecular weight fluorine-containing elastomer to a dehydrofluorination reaction with an alcohol solution of potassium hydroxide to produce a fluorine-containing elastomer having an unsaturated bond.
【０００６】[0006]
【発明の実施の形態】含フッ素エラストマーとしては、
一般にフッ化ビニリデン-ヘキサフルオロプロペン共重
合体が用いられる。その共重合割合は、ヘキサフルオロ
プロペン[HFP]に対してフッ化ビニリデン[VdF]が約3〜
5.5、好ましくは約3.2〜3.4のモル比の範囲内にある。
共重合体中には、更にテトラフルオロエチレン、エチレ
ン、プロピレン、アルキルビニルエーテル、ヘキサフル
オロイソブテン、酢酸ビニル等のフッ素化オレフィン、
オレフィン、ビニル化合物等が共重合されていてもよ
い。BEST MODE FOR CARRYING OUT THE INVENTION As the fluorine-containing elastomer,
Generally, a vinylidene fluoride-hexafluoropropene copolymer is used. The copolymerization ratio of hexafluoropropene [HFP] to vinylidene fluoride [VdF] is about 3 to
5.5, preferably within a molar ratio of about 3.2 to 3.4.
In the copolymer, further fluorinated olefins such as tetrafluoroethylene, ethylene, propylene, alkyl vinyl ether, hexafluoroisobutene, vinyl acetate,
An olefin, a vinyl compound, or the like may be copolymerized.
【０００７】これらの含フッ素エラストマーは、それの
重量平均分子量Mwが1.0×105〜5.0×105、また数平均分
子量Mnが0.3×105〜2.0×105の範囲内にある低分子量の
ものが用いられる。分子量がこれ以上のものを用いる
と、張力、伸び、永久伸び等の機械的特性が低下するよ
うになり好ましくない。These fluorine-containing elastomers have a low molecular weight having a weight average molecular weight Mw of 1.0 × 10 5 to 5.0 × 10 5 and a number average molecular weight Mn of 0.3 × 10 5 to 2.0 × 10 5 . Things are used. If the molecular weight is higher than this, the mechanical properties such as tension, elongation, permanent elongation and the like are undesirably reduced.
【０００８】含フッ素エラストマー中への不飽和結合の
生成は、水酸化カリウムのアルコール溶液による脱フッ
化水素化反応によって行われる。その反応温度は、室温
乃至約70℃、好ましくは室温乃至50℃である。アルコー
ル溶液としては一般にエタノール、メタノールの少なく
とも一種あるいはこれらとアセトンとの混合溶液などが
用いられる。使用される水酸化カリウム量およびアルコ
ール量によって不飽和結合の生成量は異なり、その値は
約50%程度に迄種々変えることができる。得られる不飽
和結合を有する含フッ素エラストマーを耐熱性を有する
接着剤組成物の有効成分として用いる場合には、その不
飽和結合含有率は4〜46%の範囲内にあることが好まし
い。[0008] The generation of unsaturated bonds in the fluorine-containing elastomer is carried out by a dehydrofluorination reaction using an alcohol solution of potassium hydroxide. The reaction temperature is between room temperature and about 70 ° C, preferably between room temperature and 50 ° C. As the alcohol solution, generally, at least one of ethanol and methanol or a mixed solution of these with acetone is used. The amount of unsaturated bond formed differs depending on the amount of potassium hydroxide and the amount of alcohol used, and the value can be varied up to about 50%. When the obtained fluorine-containing elastomer having an unsaturated bond is used as an active ingredient of an adhesive composition having heat resistance, the unsaturated bond content is preferably in the range of 4 to 46%.
【０００９】このような不飽和結合含有含フッ素エラス
トマーを接着性成分とする接着剤組成物は、一般に固形
分濃度が約1〜50重量%、好ましくは約20〜30重量%の有
機溶剤溶液として調製される。有機溶剤としては、アセ
トン、メチルエチルケトン、酢酸エチル等が用いられ
る。The adhesive composition containing such an unsaturated bond-containing fluorine-containing elastomer as an adhesive component is generally prepared as an organic solvent solution having a solid content of about 1 to 50% by weight, preferably about 20 to 30% by weight. Prepared. As the organic solvent, acetone, methyl ethyl ketone, ethyl acetate and the like are used.
【００１０】このように一般に有機溶剤溶液として調製
される接着剤組成物中には、ポリアミン化合物、例えば
m-キシリレンジアミン、ジアミノジフェニルスルホン、
ジアミノジフェニルメタン等の硬化剤が、接着性成分10
0重量部当り約0.05〜50重量部、好ましくは約0.2〜20重
量部程度添加される。硬化剤のこれ以上の割合での添加
は、かえって接着強度の低下をもたらし、特に被着物が
ポリイミドフィルムの場合には被着物フィルムの劣化を
もたらすようになる。[0010] In the adhesive composition thus generally prepared as an organic solvent solution, a polyamine compound such as
m-xylylenediamine, diaminodiphenyl sulfone,
A curing agent such as diaminodiphenylmethane is used for the adhesive component 10
About 0.05 to 50 parts by weight, preferably about 0.2 to 20 parts by weight, is added per 0 parts by weight. If the curing agent is added at a higher ratio, the adhesive strength is rather reduced, and particularly when the adherend is a polyimide film, the adherend film is deteriorated.
【００１１】また、接着剤組成物中には、硬化剤を完全
に作用させ、それによって硬度を上げる目的でエポキシ
樹脂も添加される。エポキシ樹脂としては、ビスフェノ
ールA型、ビフェニル型、グリシジルアミン型、ノボラ
ック型等の任意のものが、接着性成分100重量部当り約1
〜50重量部、好ましくは約2〜20重量部の割合で用いら
れる。An epoxy resin is also added to the adhesive composition for the purpose of making the curing agent act completely and thereby increasing the hardness. As the epoxy resin, any of bisphenol A type, biphenyl type, glycidylamine type, novolak type, etc. may be used in an amount of about 1 per 100 parts by weight of the adhesive component.
To 50 parts by weight, preferably about 2 to 20 parts by weight.
【００１２】これらの各添加剤の少なくとも一種を配合
した接着剤組成物は、その有機溶剤溶液を被着体に塗布
し、約50〜185℃の温度条件下で有機溶媒を揮散させた
後、約150〜180℃の温度条件下で約10〜20分間程度キュ
アさせることにより硬化させることができる。この接着
剤組成物がプリント基板等の電子材料用接着剤として用
いられる場合には、有機溶媒を揮散させてポリテトラフ
ルオロエチレンフィルム、ポリアミドフィルム上等に接
着剤層を約25μm程度の膜厚で形成させた後、そこに銅
箔を貼り合わせ、プレスした後キュア条件下での硬化処
理が行われる。An adhesive composition containing at least one of these additives is prepared by applying an organic solvent solution to an adherend and volatilizing the organic solvent at a temperature of about 50 to 185 ° C. The composition can be cured by curing at a temperature of about 150 to 180 ° C. for about 10 to 20 minutes. When this adhesive composition is used as an adhesive for electronic materials such as printed circuit boards, an organic solvent is volatilized to form an adhesive layer having a thickness of about 25 μm on a polytetrafluoroethylene film, a polyamide film, or the like. After the formation, a copper foil is bonded thereto and pressed, followed by a curing treatment under curing conditions.
【００１３】[0013]
【発明の効果】本発明に係る不飽和結合を有する含フッ
素エラストマーは、それを耐熱性が要求される接着剤組
成物の接着性成分として用いることができ、それが本来
有する良好な耐熱性に加えて、特に張力等の機械的特性
の点においてすぐれているという特徴を有している。Industrial Applicability The fluorine-containing elastomer having an unsaturated bond according to the present invention can be used as an adhesive component of an adhesive composition which requires heat resistance. In addition, it is characterized by being excellent in mechanical properties such as tension.
【００１４】[0014]
【実施例】次に、実施例について本発明を説明する。Next, the present invention will be described by way of examples.
【００１５】実施例１ 容量250mlの三口フラスコに、低分子量VdF-HFP(共重合
モル比3.2：1)共重合体(重量平均分子量Mw＝1.2×105、
数平均分子量Mn＝0.5×105)25gを仕込み、そこにアセト
ン58mlとエタノール28mlとの混合溶媒を加えて攪拌す
る。更に、水酸化カリウム0.38gをエタノールに溶解さ
せた25重量%溶液を加え、室温条件下で6時間攪拌した
後、攪拌を止めて一夜放置した。Example 1 A low molecular weight VdF-HFP (copolymerization molar ratio of 3.2: 1) copolymer (weight average molecular weight Mw = 1.2 × 10 5 ,
25 g of number average molecular weight Mn = 0.5 × 10 5 ) is charged, and a mixed solvent of 58 ml of acetone and 28 ml of ethanol is added thereto and stirred. Further, a 25% by weight solution of 0.38 g of potassium hydroxide dissolved in ethanol was added, and the mixture was stirred for 6 hours at room temperature, then stopped stirring and left overnight.
【００１６】若干着色した溶液をロ過し、ロ液の５倍量
の蒸留水で共重合体を再沈させ、再沈した共重合体を取
り出し、手で絞って水を切ってから、アセトン58mlに溶
解させた。アセトン溶液からの水による再沈を２回くり
返した後、沈殿物を30重量%アセトン溶液として調製
し、これを激しく攪拌しながら３倍量のエタノール中に
注いだ。この沈殿物をポリエチレンフィルム上に載せ、
約50〜60℃で24時間乾燥し、若干着色したアルカリ処理
共重合体を23.7g得た。赤外線吸収スペクトルおよび19F
-NMRによってそれの二重結合含有率を測定すると、その
値は4%であった。The slightly colored solution was filtered, the copolymer was reprecipitated with 5 times the volume of distilled water, the reprecipitated copolymer was taken out, squeezed by hand to drain the water, and then acetone Dissolved in 58 ml. After the reprecipitation with water from the acetone solution was repeated twice, the precipitate was prepared as a 30% by weight acetone solution, and poured into a three-fold amount of ethanol with vigorous stirring. Put this precipitate on a polyethylene film,
After drying at about 50-60 ° C for 24 hours, 23.7 g of a slightly colored alkali-treated copolymer was obtained. Infrared absorption spectrum and 19 F
Its double bond content was measured by NMR to be 4%.
【００１７】実施例２〜６ 実施例１において、アセトン58mlとの混合溶媒中のエタ
ノール量(EtOH)および25重量%エタノール溶液として調
製される水酸化カリウム量(KOH)を種々に変化させる
と、次の表１に示されるような結果が得られた。なお、
二重結合含有率が増加するに従って、アルカリ処理共重
合体の着色度は次第に高くなった。 表１ 実施例 EtOH(g) KOH(g) 収量(g) 二重結合含有率(%) ２ 27 0.75 23.5 8 ３ 25 1.25 23.2 11 ４ 23 2.0 22.5 17 ５ 17 4.0 22.5 28 ６ 5 8.0 21.5 46Examples 2 to 6 In Example 1, the amount of ethanol (EtOH) in a mixed solvent with 58 ml of acetone and the amount of potassium hydroxide (KOH) prepared as a 25% by weight ethanol solution were variously changed. The results as shown in the following Table 1 were obtained. In addition,
As the double bond content increased, the degree of coloration of the alkali-treated copolymer gradually increased. Table 1 Example EtOH (g) KOH (g) Yield (g) Double bond content (%) 2 27 0.75 23.5 8 3 25 1.25 23.2 11 4 23 2.0 22.5 17 5 17 4.0 22.5 28 6 5 8.0 21.5 46
【００１８】なお、実施例１〜６における赤外線吸収ス
ペクトル(FT-IR)の測定は、Specord75を用いて行われ
た。測定サンプルは、厚さ0.05mmのフィルム状にプレス
成形され、PTFE補償によって測定された。吸収スペクト
ルの特性値は、次の如くである。 C-H結合：3016〜2970cm~1 3016cm~1における吸収は次第に消える 2970cm~1における吸収の強度は次第に増える 2930cm~1に吸収が現われ、その吸収の強度は次第に増え
る 2890cm~1に吸収が現われ、その吸収の強度は次第に増え
る C=C結合：1712〜1624cm~1に３つの強い吸収が現われ、
それぞれの吸収の強度は1712、1676および1624cm~1の順
で次第に変わるIn addition, the infrared absorption switches in Examples 1 to 6 were used.
The spectrum (FT-IR) is measured using Specord75.
Was. The measurement sample is pressed into a 0.05mm thick film
Molded and measured by PTFE compensation. Absorption spectrum
The characteristic values of the file are as follows. C-H bond: 3016-2970cm ~1 3016cm ~1Absorption gradually disappears from 2970cm ~1The intensity of absorption in the area gradually increases from 2930cm ~1And the intensity of the absorption gradually increases
2890cm ~1And the intensity of the absorption gradually increases
C = C bond: 1712-1624cm ~1Three strong absorptions appear
The intensity of each absorption is 1712, 1676 and 1624cm ~1Order
Changes gradually
【００１９】また、19F-NMRの測定は、内部標準試料と
してCFCl3を用い、470.6MHzのBrukerAM-500機器を用い
て、d-アセトン溶媒中で行われた。水酸化カリウムによ
る二重結合形成反応では、次の４種類の反応生成物が考
えられ、フッ素5の共鳴は69〜75ppm(69.6，74.1，74.5)
に、またフッ素1〜4の共鳴は52〜62ppm(52.6，55.8，5
8.5，62.0)にそれぞれ現われる。 The measurement of 19 F-NMR was carried out in a d-acetone solvent using a 470.6 MHz Bruker AM-500 instrument, using CFCl 3 as an internal standard sample. In the double bond formation reaction with potassium hydroxide, the following four reaction products are considered, and the resonance of fluorine 5 is 69 to 75 ppm (69.6, 74.1, 74.5).
And the resonance of fluorine 1-4 is 52-62 ppm (52.6, 55.8, 5
8.5, 62.0) respectively.
【００２０】二重結合含有率は、フッ素5およびフッ素1
〜4のケミカルシフトの積分値からも計算された。 モノマーユニット含有量(%) 実施例 二重結合含有率(%) Σp Σq Σr (原料) 0 0 24 76 １ 4 1 23 76 ２ 8 2 22.5 75.5 ３ 11 3 21.5 75.5 ４ 17 4 21 75 ５ 28 7 19 74 ６ 46 12 15 73 The double bond content is determined by fluorine 5 and fluorine 1
It was also calculated from the integrated values of ~ 4 chemical shifts. Monomer unit content (%) Example double bond content (%) .SIGMA.p [sum] Q? R (material) 0 0 24 76 1 4 1 23 76 2 8 2 22.5 75.5 3 11 3 21.5 75.5 4 17 4 21 75 5 28 7 19 74 6 46 12 15 73
【００２１】比較例 低分子量VdF-HFP(共重合モル比3.7〜4.0：1)共重合体(M
w：4.0〜6.0×105、Mn：1〜2×105)10gをメチルイソブ
チルケトン200mlに溶解させた溶液に、水酸化バリウム3
gおよびベンジルトリフェニルホスホニウムクロライド
0.1gを蒸留水100mlに溶解させた水溶液を滴下し、滴下
終了後15℃で2時間攪拌する。Comparative Example A low molecular weight VdF-HFP (copolymer molar ratio of 3.7 to 4.0: 1) copolymer (M
w: 4.0 to 6.0 × 10 5 , Mn: 1 to 2 × 10 5 ) A solution of 10 g in 200 ml of methyl isobutyl ketone was added with barium hydroxide 3
g and benzyltriphenylphosphonium chloride
An aqueous solution obtained by dissolving 0.1 g in 100 ml of distilled water is added dropwise, and after completion of the addition, the mixture is stirred at 15 ° C. for 2 hours.
【００２２】反応混合物をn-ヘキサンによって再沈し、
沈殿物を50℃で一夜減圧乾燥する。生成物の二重結合含
有率を19F-NMRによって測定すると、55%であった。ま
た、FT-IR測定では、1750、1720および1680cm~1に３つ
の強いC=C結合の吸収がみられた。ただし、この二重結
合含有低分子量VdF-HFP共重合体には、格別の機械的特
性(張力、伸び、単位伸びおよび接着強度)が認められな
かった。The reaction mixture is reprecipitated with n-hexane,
The precipitate is dried under reduced pressure at 50 ° C. overnight. The double bond content of the product was determined by 19 F-NMR to be 55%. In the FT-IR measurement, three strong C = C bond absorptions were observed at 1750, 1720, and 1680 cm- 1 . However, no extraordinary mechanical properties (tensile force, elongation, unit elongation, and adhesive strength) were observed in the low molecular weight VdF-HFP copolymer containing a double bond.
【００２３】実施例７ 下記(a)成分および(b)成分の混合物からなる接着剤組成
物が調製された。 (a)成分：種々の二重結合含有率を有する低分子量VdF-H
FP共重合体(Mw:2.0×105、Mn:1.5×105)100重量部およ
び所定量のビスフェノールA型エポキシ樹脂(油化シェル
エポキシ製品ED-20；エポキシ当量約200)をメチルエチ
ルケトン溶媒に溶解させた溶液 (b)成分：2,4,6-トリ(ジメチルアミノメチル)フェノー
ル硬化剤をメチルエチルケトン溶媒に溶解させた溶液Example 7 An adhesive composition comprising a mixture of the following components (a) and (b) was prepared. Component (a): Low molecular weight VdF-H having various double bond contents
100 parts by weight of an FP copolymer (Mw: 2.0 × 10 5 , Mn: 1.5 × 10 5 ) and a predetermined amount of a bisphenol A type epoxy resin (oiled shell epoxy product ED-20; epoxy equivalent: about 200) were dissolved in methyl ethyl ketone solvent Dissolved solution (b) Component: Solution in which 2,4,6-tri (dimethylaminomethyl) phenol curing agent is dissolved in methyl ethyl ketone solvent
【００２４】調製された接着剤組成物を、ポリイミドフ
ィルム基質上に塗布し、室温下で48時間、次いで130℃
で１時間硬化させた後、室温下に７日間以上放置し、基
質から剥離してフィルムを得た。得られた各フィルムに
ついて、JIS K-6301の測定法に従って、張力、伸びおよ
び永久伸びを測定した。The prepared adhesive composition is applied on a polyimide film substrate, and then left at room temperature for 48 hours and then at 130 ° C.
After curing for 1 hour at room temperature, the film was left at room temperature for 7 days or more and peeled from the substrate to obtain a film. For each of the obtained films, the tension, elongation and permanent elongation were measured according to the measuring method of JIS K-6301.
【００２５】得られた結果は、次の表に示される。 表 共重合体 エポキシ 固形分 測定値 二重結合 樹脂 硬化剤 濃度 張力 伸び 永久伸び No. (%) (重量部) (重量部) (重量%) (MPa) (%) (%) １ 0 20 3.5 0.6 565 ２ 8 〃 〃 4.3 550 27 ３ 11 〃 〃 5.8 430 22 ４ 17 〃 〃 5.2 390 24 ５ 28 〃 〃 8.9 220 10 ６ 46 〃 〃 10.5 130 5 ７ 28 10 0.8 32 4.1 460 22 ８ 〃 〃 1.7 〃 7.2 350 12 ９ 〃 〃 2.8 34 8.8 280 11 10 〃 〃 5.2 33 9.7 220 10 11 〃 〃 3.0 43 8.5 215 〃 12 〃 20 〃 40 7.3 175 〃 13 〃 30 〃 37 8.4 125 5 14 〃 40 3.3 32 9.0 70 9 15 〃 50 3.8 28 8.5 40 6 The results obtained are shown in the following table. Table Copolymer Epoxy Solidsmeasured value Double bond Resin Hardener concentration Tension elongation Permanent elongation No. (%) (Weight parts) (Weight parts) (weight%) (MPa) (%) (%) 1 0 20 3.5 0.6 565 28 〃 〃 4.3 550 273 11 11 5.8 5.8 430 22 417 〃 〃 5.2 390 24 528 〃 〃 8.9 220 10 6 46 〃 〃 10.5 130 5 7 28 10 0.8 32 4.1 460 228 〃 〃 1.7 〃 7.2 350 12 9 〃 〃 2.8 34 8.8 280 11 10 〃 〃 5.2 33 9.7 220 10 11 〃 〃 3.0 43 8.5 215 〃 12 〃 20 〃 40 7.3 175 〃 13 〃 30 〃 37 8.4 125 5 14 〃 40 3.3 32 9.0 70 9 15 〃 50 3.8 28 8.5 40 6
【００２６】実施例８ 二重結合含有率20%の低分子量VdF-HFP共重合体(Mw:5×1
05、Mn:2.0×105)6gおよびビスフェノールA型エポキシ
樹脂(ED-20)0.6gを酢酸エチル17gに溶解させた溶液と、
2,4,6-トリ(ジメチルアミノメチル)フェノール硬化剤1.
15gを溶解させた13重量%酢酸エチル溶液とを混合し、接
着剤組成物を調製する。Example 8 A low molecular weight VdF-HFP copolymer having a double bond content of 20% (Mw: 5 × 1
0 5 , Mn: 2.0 × 10 5 ) 6 g and a solution of 0.6 g of bisphenol A type epoxy resin (ED-20) dissolved in 17 g of ethyl acetate,
2,4,6-tri (dimethylaminomethyl) phenol curing agent 1.
An adhesive composition is prepared by mixing 15 g of a 13 wt% ethyl acetate solution in which 15 g is dissolved.
【００２７】この接着剤組成物をポリイミドフィルム(2
0×10cm)上に塗布し、室温下で20分間風乾した後、更に
100℃で7分間乾燥させ、膜厚約30〜40μmの接着剤層を
形成させた。これを銅箔に貼り合わせ、プレスした後、
180℃で10分間キュアした。このときの接着強度は、1.6
kg/cmであった。また、キュア条件を150℃で15分間に変
更すると、接着強度は、1.2kg/cmであった。This adhesive composition was applied to a polyimide film (2
0 × 10cm) and air-dried at room temperature for 20 minutes.
After drying at 100 ° C. for 7 minutes, an adhesive layer having a thickness of about 30 to 40 μm was formed. After bonding this to copper foil and pressing,
Cure at 180 ° C. for 10 minutes. The bonding strength at this time is 1.6
kg / cm. When the curing conditions were changed to 150 ° C. for 15 minutes, the adhesive strength was 1.2 kg / cm.
【００２８】更に、実施例７のNo.1〜15の接着剤組成物
を用いて、銅箔との間の接着強度を測定すると、共重合
体の二重結合含有率、組成比、乾燥条件およびキュア条
件などによって接着強度の値は変わるものの、いずれも
約1.2〜1.9kg/cmの範囲内にあった。Further, the adhesive strength between the adhesive composition and the copper foil was measured using the adhesive compositions Nos. 1 to 15 of Example 7, and the double bond content, the composition ratio, and the drying conditions of the copolymer were measured. Although the value of the adhesive strength changed depending on the curing conditions and the like, all were within the range of about 1.2 to 1.9 kg / cm.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 林 正添 茨城県北茨城市華川町臼場577 (72)発明者 達 春美 茨城県日立市弁天町３−８−４ (72)発明者 レフ モイセーイエビッチ コーガン ロシア連邦共和国 サンクト ペテルブル ク市 198207 プロスペクト レーニンス キー120 クバルティーラ130 (72)発明者 アナトーリー ステパーナビッチ スコル ニャコフ ロシア連邦共和国 サンクト ペテルブル ク市 194355 ウリツァ コンポジートロ フ19 クバルティーラ129 (72)発明者 タチヤーナ ボリソヴナ ザペワロワ ロシア連邦共和国 サンクト ペテルブル ク市 194356 ウリツァ ルナチャールス キー42−２ クバルティーラ24 (72)発明者 オリガ ビクトリーノヴナ ブラゴダトワ ロシア連邦共和国 サンクト ペテルブル ク市 191126 ウリツァ ソツィアリスチ ーチェスカヤ７ クバルティーラ６ (72)発明者 セルゲイ バシリエビッチ ソコロフ ロシア連邦共和国 サンクト ペテルブル ク市 198217 プロスペクト ダーチヌイ 19−１ クバルティーラ222 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masazo Hayashi 577 Usuba, Hachikawa-cho, Kitaibaraki-shi, Ibaraki (72) Inventor Harumi 3-8-4 Bentencho, Hitachi-shi, Ibaraki (72) Inventor Ref Moi Sayevich Kogan Russia St. Petersburg 198207 Prospect Lenin's Quay 120 Kubartila 130 (72) Inventor Anatoly Stephanavich Skol Nyakov Russia St. Petersburg 194 355 Urica Composite Trokh 19 Kubartila 129 (72) Inventor Tatjana Borisovna Zapewarova, St. Petersburg, Russia 194356 Ulica Lunachars Quay 42-2 Kubartila 24 (72) Inventor Olga Victory Novna Bra Datowa Russian Federal Republic of St. Peteruburu click City 191,126 Uritsua Sotsuiarisuchi Chesukaya 7 Kubarutira 6 (72) inventor Sergei Bashiriebitchi Sokolov Russian Federation Republic St. Peteruburu click City 198 217 Prospect Dachinui 19-1 Kubarutira 222
Claims (5)
カリウムのアルコール溶液によって脱フッ化水素化反応
させることを特徴とする不飽和結合を有する含フッ素エ
ラストマーの製造法。1. A method for producing a fluorine-containing elastomer having an unsaturated bond, comprising subjecting a low-molecular-weight fluorine-containing elastomer to a dehydrofluorination reaction with an alcoholic solution of potassium hydroxide.
合を有する含フッ素エラストマーを接着性成分とする接
着剤組成物。2. An adhesive composition comprising the fluorine-containing elastomer having an unsaturated bond obtained by the method according to claim 1 as an adhesive component.
加された請求項２記載の接着剤組成物。3. The adhesive composition according to claim 2, further comprising a polyamine compound as a curing agent.
記載の接着剤組成物。4. The method according to claim 2, wherein an epoxy resin is further added.
The adhesive composition as described in the above.
４のいずれかに記載された接着剤組成物。5. The method according to claim 2, which is used for bonding an electronic material.
5. The adhesive composition according to any one of 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08761397A JP3664565B2 (en) | 1997-02-18 | 1997-03-21 | Method for producing fluorine-containing elastomer having unsaturated bond |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4983697 | 1997-02-18 | ||
| JP9-49836 | 1997-02-18 | ||
| JP08761397A JP3664565B2 (en) | 1997-02-18 | 1997-03-21 | Method for producing fluorine-containing elastomer having unsaturated bond |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10292010A true JPH10292010A (en) | 1998-11-04 |
| JP3664565B2 JP3664565B2 (en) | 2005-06-29 |
Family
ID=26390287
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08761397A Expired - Fee Related JP3664565B2 (en) | 1997-02-18 | 1997-03-21 | Method for producing fluorine-containing elastomer having unsaturated bond |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010244982A (en) * | 2009-04-09 | 2010-10-28 | Tozai Co Ltd | Mica heater |
| JP2010282936A (en) * | 2009-06-08 | 2010-12-16 | Tozai Co Ltd | Collected mica plate |
| JP2020090564A (en) * | 2018-12-03 | 2020-06-11 | 日本メクトロン株式会社 | Adhesive film, adhesive composition, and flexible printed circuit board |
| JP2021513592A (en) * | 2018-02-12 | 2021-05-27 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Fluoroelastomer curable composition |
| JP2021091873A (en) * | 2019-12-02 | 2021-06-17 | 日本メクトロン株式会社 | Adhesive film and flexible printed board |
-
1997
- 1997-03-21 JP JP08761397A patent/JP3664565B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010244982A (en) * | 2009-04-09 | 2010-10-28 | Tozai Co Ltd | Mica heater |
| JP2010282936A (en) * | 2009-06-08 | 2010-12-16 | Tozai Co Ltd | Collected mica plate |
| JP2021513592A (en) * | 2018-02-12 | 2021-05-27 | ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． | Fluoroelastomer curable composition |
| JP2020090564A (en) * | 2018-12-03 | 2020-06-11 | 日本メクトロン株式会社 | Adhesive film, adhesive composition, and flexible printed circuit board |
| JP2021091873A (en) * | 2019-12-02 | 2021-06-17 | 日本メクトロン株式会社 | Adhesive film and flexible printed board |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3664565B2 (en) | 2005-06-29 |
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